Disazo pyrazolyl dyestuffs



United States Patent 3,325,468 DESAZO PYRAZOLYL DYESTUFFS Jean-PierreJung, Riehen, near Base], and Guido Schetty, Basel, Switzerland,assignors, by mesne assignments, to H. A. Whitten 8: (10., New York,N.Y., a partnership No Drawing. Original application Dec. 10, 1962, Ser.No. 243,62tB, now Patent No. 3,197,455, dated July 27, 1965. Divided andthis application July 3,1963, Ser. No. 327,164 Claims priority,application Switzerland, Dec. 15, 1961, 14,557/61 Claims. (Cl. 260-160)The present application is a division of copending application, Ser. No.243,620, filed Dec. 10, 1962 now US. Patent No. 3,197,455.

The present invention concerns new disazo dyestuffs, processes for theproduction thereof, processes for the dyeing of fibres containingnatural or synthetic polypeptide as well as, as industrial product, thematerial fast dyed with the aid of these dyestuffs.

It has been found that valuable dyestuffs are obtained by coupling (a)two mols of a diazotised, negatively substituted amine D-NH of thebenzene series,

(b) with one mol of a coupling component of the Formula I GH|-C=N SONHSO N=CCH3 HC==C C=CH I Z Z I NH: NH: (I)

to form a disazo dyestulf of the general Formula II CHa-C= SOzNHSO;/N=C-CHs a D-N=NO=(IJ Z Z (|]=ON=N-D NH: NH: (II) with the proviso thatthe total number of water-solubilizing groups is at least 1 andmaximally 4.

D in Formula II represents an unsulfonated or monosulfonated phenylradical with from one to two negative substituents and which can containfurther substituents 1 compatible with azo dyestuffs. In thisspecification and in the appended claims negative substituents in D meanthe following substituents: trifiuoromethyl, cyano and, especially thosewhich contain an oxygen atom and the bond of which between the linkingatom and the oxygen is semipol'ar, namely, the nitro, carb-oxy, loweralkyl-carbonyl, lower alkoxy carbonyl, as well as, in a preferred groupof dyestuffs according to the invention, the sulphonyl-containing groupof the formula in which R is hydroxyl, phenyl, methylphenyl,chlorophenyl, phenoxy, methylphenoxy, chlorophenoxy, bromophenoxy,chloroacetylaminophenoxy, N-lower alkyl-N- phenyl-amino, and Z ispreferably H, or chloro, bromo, methyl, ethyl or 40 E with the provisothat the total number of --SO H groups is maximally 4.

Lower alkyl as used in this specification means alkyl with from 1 to 5carbon atoms.

As additional substituents, the phenyl radical of the diazo components Dusable according to the invention can also contain the followingsubstituents compatible with az-o dyestuffs: lower alkyl groups such asmethyl, ethyl, nor tert. butyl or tert. amyl; the benzyl, methylbenzylor chlorobenzyl group; phenyl, lower alkyl phenyl, chloro phenyl, orbromophenyl; lower :allroxy groups such as methoxy, ethoxy, or butoxy;the benzyloxy group; phenoxy, alkylphenoxy with alkyl of maximally 8carbon atoms, chlorophenoxy, bromophenoxy, phenylthio, alkylphenylthiowith alkyl of maximally 8 carbon atoms, chlorophenylthio, orbromophenyl-thio; acylamino groups such as acetylamino,chloroacetylamino, fi-bromopropionylamino, phenacetylamino,phenoxyacetylamino, benzoxylamino, chlorobenzoylamino, a triazinylaminoor a dichloropyrimidylamino group; lower carbalkoxyamino groups such asthe carbomethoxyamino, carboethoxyamino, carbobutoxyamino,carbocyclohexylamino group; finally chlorine, fluorine or bromine.

Particularly suitable diazo components are aminobenzene sulphonic acids,aminodiphenyl sulphones, aminobenzene sulphonic acidN-alkyl-N-phenyl-amides as well as aminodiphenylethers wherein allphenyl radicals can be free from or can contain sulphonic acid groups.The diazotisation is performed in a known way, for example, in mineralacid, aqueous solution with the alkali metal salts of nitrous acid or inconcentrated sulphuric acid with nitrosyl sulphuric acid.

The coupling components of the above Formula I usable according to theinvention are bis-(pyrazolyl-phenyl)- disulphimides such as bis-[2-, 3-or 4- (3' methyl 5famino-pyrazolyl-(1')) phenyl] disulphimide. Thesecoupling components are new and they are obtained, for example, bycondensing 2 mols of cyanoacetone or cyanoacetoneimine by known methodspreferably in mineral acid, aqueous solution with a bis-hydrazine ofFormula III SOgNHSO:

(Ill)- wherein Z has the meaning given in Formula II.

The diazotised amine is coupled at a temperature of about 10 to +50 C.and preferably at +10 to 25 C. with the bis-pyrazolyl compound ofFormula I as defined above, advantageously in an aqueous-acid medium,while, if desired, gradually buffering the acid with an agent whichraises the pH value, eg with an alkali metal salt of a low-molecularfatty acid such as sodium acetate and, if necessary, in the presence oforganic solvents which are miscible with water such as low fatty acids,e.g. acetic acid, low fatty alcohols, e.g. methanol or ethanol or lowaliphatic ketones such as acetone or also dioxan.

A modification of the process for the production of disazo dyestuffsaccording to the invention consists in coupling one mol of a diazotised,negatively substituted amine D-NH of the benzene series with one mol ofa compound of Formula 1V CHt-fJ-GHr-CN wherein M represents the 0x0 orthe imino group, to formv a monoazo dyestutf of Formula V CH:C'CH-CN MN:ND (V) wherein D has the meaning given in Formula II, and con- OMS-Qdensing two mols of the monoazo dyestulf so obtained, in

an acid aqueous medium, with one mol of a bis-hydrazine of Formula IIIto form a disazo dyestulf of Formula II. I The disazo dyestuffs ofFormula II produced according to the invention are isolated in the formof their ammonium or alkali metal salts. As such they are yellow, orangeto brown powders. They are excellently suitable for the dyeing andprinting of natural and synthetic poly-peptide fibres such as leather,silk or, principally, wool as well as of synthetic polyamide andpolyurethane fibres such as nylon or Perlon. The dyeings obtained onthese fibres are usually distinguished by the purity of their greenishyellow, yellow or orange shades, a food fastness to light and excellentfastness to alkali. They dr-aw onto wool from a neutral to weakly acidbath and the wool dyeings obtained have very good fastness to washing,milling, sea water, chlorine, and rubbing.

Particularly those new disazo dyestuffs of Formula II according to theinvention wherein D-NH is an o-aminodiphenyl sulphone radical arepreferred because of their 40 excellent fastness to light and excellentfastness in the other above-listed wet treatments Those wherein DNH is am-aminobenzene sulphonylor a m-aminobenzene carbonyl radical arepreferred because of their very pure,

very greenish-yellow shade, and are therefore very val- 45 uable ascombination dyestuffs, since they can be combined well with pure bluedyestuffs to give brilliant green shades.

Further details can be seen from the following exam- 4 ples. Where nototherwise expressly stated, parts are given as parts by weight. Thetemperatures are in degrees centigrade. The relationship of parts byweight to parts by volume is as that of grams to cubic centimeters.

Example 1 24.9 parts of Z-arninobenzene-l-sulphonic acid phenyl esterare suspended in 180 parts of glacial acetic acid, dissolved by thedropwise addition of 30 parts of concentrated hydrochloric acid anddiazotized at 0-10" by the addition of 6.9parts of sodium nitrite in 20parts of ester. The diazo solution is slowly poured at 0-5 into asolution of 21.9 parts of bis-[3-(3-methyl-5'-amino pyrazolyl-(1))-phenyl]-disu1phimide and 25 parts of crystallized sodium acetate in600 parts of water. The mixture is poured for several hours at 0l0, 100parts of sodium chloride are added, the precipitated dyestuff isfiltered off and dried.

It is a yellow powder which dissolves in hot water with agreenish-yellow color. It dyes wool on boiling from a neutral to weaklyacid bath containing ammonium sulphate in pure yellow very level shadeswhich are fast to wet and light. The bath is well exhausted.

The bis [3 (3' methyl 5 amino pyrazolyl-(1))- phenyl]-disulphimide usedas coupling component is obtained by reacting 1 mol of3,3'-bis-hyd-razino-1,1'-diphenyl disulphimide with 2 mols ofcyanoacetone imino in a hydrochloric acid aqueous solution.

Further dyestuffs according to the invention are given in the followingTable I which are produced by using corresponding amounts of diazo andcoupling components according to the methods described in Example 1.

TABLE I No. Diazo component Coupling component Shade of wool dyeing 1.z-amluo 1,1'-dlphenylsulphoneBls-gg-(3'-methyl-5'-amlnopyrazolyl-(l))-pheny1]-dlsulphl- Yellow.

m e. 2 3-arni r(i1obenzene-l-sulphonlc acid-N-ethyl-N-phenyldn Greenlshyellow.

arm a. 3 4-aninobenzene-l-sulphonic acid-(2-methylphenyl)- do. Yellow.

es er. 2-amino-4-methyl-1,1 -diphenyl-disulphimide D o.zraminobenzene-l-sulphonic acid do Do. 4-amin0-diphenyl ether3-sulphonic acid Bis- B-fiigrlreitiyl-b aminopyraz0lyl-(1))-4-cl1l0rophenyl]- Yellow.

lsu p e. 3-amino-benzene-l-sulphonic acid phenyl ester- Big l3-1(ilgineitgiyl-o-amino-pyrazolyl-(1))-4-methylphenyl]- Greenish yellow.lSl] p m e. 8 rln Bis-[13$ngthyl-o-amlnopyrazolyl-(1))4-ethylphenyl]-dl- Do.

. 'su p m e. 9 2-amlno-1-1-diphenylsulphone-3-sulphonlc acidBls-[4-(3-methyl-5-aminopyrazolyl-(1))-3-methyl-5-chloro- Yellow.

phenyll-disulphlmide. 10 .doBis-[4-(3-methyl-5-amlnopyrazolyl-(1'))-2-5-dichlor0pl1e11yl]- Do.

. disulphimide. 4-aminobenzene-l-sulphonlc acld-N-ethyl-N-4-sulpho-Bis-[4-(3-methyl-5-amlnopyrazolyl-(1'))-2-methyl-5-chloro- Do. 1phenylarnide. phenyll-disulphlmlde.

n Bis-[3- (3 @methyl-Ev -aminopyrazolyl-(1) )-4-brorn0phenyl]- D o.

' I disulphimide. 2-amlnobenzene-l-sulphonlc acid phenyl esterBE:[4-1(3;;Efit;iyl-5'-aminopyrazolyl-(1))-2-5-dlbrom0phenyl]- Do.

- 1511 p e. 2-amlno-1-but0xycarbonylbenzeneBis-[3-(3-methyl-5-amlnopyrazo1yl-(1)-4-sulphophenyl]- Do.

disulphimide. 3-amlno-l-amyloxycarbonylbenzenc n Greenlsh yellow.

Other diazo components which may be used in lieu of those listed in theforegoing table are:

and the phenyl nucleus of the above defined D linked directly to theadjacent azo bridge being substituted 'by a member selected from amonghydrogen and lower alkyl.

What is claimed is: 1. A disazo dyestufi of the formula 6 wherein thedyestufl molecule contains a maximum of four water-solubilizing groups,Z is a member selected from the group consisting of H, chloro, bromo,methyl, ethyl and SO H, each D is a member selected from the groupconsisting of phenoxyphenyl phenylsulfonylphenyl tmethyl-phenylsulfonylphenyl chloro-phenylsulfonylphenylphenoxyesulfonylphenyl lower alkyl-phenoxy-sulfonylphenyl chloroacetylamino-phenoxysulfony1phenyl chlorophenoxy-sulfonylphenyl N-loweralkyl-N-phenylamino-sulfonylphenyl methylphenyl-disulfimidophenylchlorophenyl-disulfimidophenyl benzoylphenyldichlorotriazinylaminophenyl lower alkoxycarbonylphenyl phenylsulfo-phenyl chloroacetylaminophenyl nitrophenyl carboxyphenyl and thephenyl nucleus of the above defined D linked directly to the adjacentazo bridge being substituted by a member selected from the groupconsisting of H and lower alkyl, each D being further substituted byfrom 0 to 1 sulfonic acid gnoup.

2. A disazo dyestuff of the formula 3. A disazo dyestuff of the formula4. A disazo dyestulf of the formula R 3,325,468 v 7 8 5. A disazodyestufi of the formula N OSOINHSO1-O No references cited.

CHARLES B. PARKER, Primary Examiner,

R. J. FINNEGAN, DONALD M. PAPUGA,

Assistant Examiners.

1. A DISAZO DYESTUFF OF THE FORMULA